Self-dimerizations of twenty three aromatic carboxylate and sulfonate ions from their electrophoretic mobilities in aqueous solution were estimated by capillary zone electrophoresis (CZE). The magnitudes of the self-dimerizations ascribed to π-π interactions of these aromatic anions were determined by CZE as dimerization constants (KD). Although the largest KD value of 1.2 dm3 mol-1 for 9-anthracenecarboxylate ion (9-AC) in these aromatic anions was found, almost all of the KD values were zero, or near to zero. It was found that the π-π interactions of the aromatic anions were relatively small at zero ionic strength, in which the contribution of an ionic association between the cation and aromatic anions could be excluded from the KD values, since the contribution of the electric repulsion between the aromatic anions on the KD values was large. The relatively large KD value of 9-AC caused that it electro-migrates as its planar shape, and has an anthracene ring of a largely hydrophobic aromatic ring.
A new, simple and rapid capillary electrophoresis (CE) method, using hexadimethrine bromide (HDB) as electroosmotic flow (EOF) modifier, was developed for the identification and quantitative determination of four plant hormones, including gibberellin A3 (GA3), indole-3-acetic acid (IAA), α-naphthaleneacetic acid (NAA) and 4-chlorophenoxyacetic acid (4-CA). The optimum separation was achieved with 20 mM borate buffer at pH 10.00 containing 0.005% (w/v) of HDB. The applied voltage was -25 kV and the capillary temperature was kept constant at 25°C. Salicylic acid was used as internal standard for quantification. The calibration dependencies exhibited good linearity within the ratios of the concentrations of standard samples and internal standard and the ratios of the peak areas of samples and internal standard. The correlation coefficients were from 0.9952 to 0.9997. The relative standard deviations of migration times and peak areas were < 1.93 and 6.84%, respectively. The effects of buffer pH, the concentration of HDB and the voltage on the resolution were studied systematically. By this method, the contents of plant hormone in biofertilizer were successfully determined within 7 min, with satisfactory repeatability and recovery.
A simple batch method for the fluorometric determination of hydrogen peroxide using phosphine-based fluorescent reagents has been developed. A rapid, mild and selective derivatization reaction was achieved by adding sodium tungstate dihydrate to the reaction mixture of hydrogen peroxide and a phosphine-based fluorescent reagent. When 4-diphenylphosphino-7-methylthio-2,1,3-benzoxadiazole was used as a reagent, the derivatization reaction was completed after 2 min at room temperature. The calibration curve was linear between 12.5 and 500 ng hydrogen peroxide in a 10 µL sample solution. This method is accurate and has potential for on-line applications.
A highly sensitive resonance Rayleigh-scattering (RRS) method for the determination of sildenafil citrate has been developed, based on the fact that sildenafil (Sild) reacted with Evans Blue (EB) to form an ion-association complex in pH 1.1 - 4.6 aqueous solution. This resulted in a significant enhancement of the RRS intensity, and a new spectrum appeared. The wavelength of the maximum RRS was at 365 nm, and other scattering peaks were at 400, 442, 470 and 534 nm, respectively. The intensity of RRS was directly proportional to the concentration of Sild in the range 0 - 11.5 µg ml-1, and the detection limit for Sild (3 σ) was 30.3 ng ml-1. The composition of the ion-association complex was Sild:EB = 1:1, as established by Job's method. The method had good selectivity and could be applied to the determination of Sild in the aqueous phase without using organic solvent extraction. The method was simple and rapid. In addition, the reaction mechanism and the reason for RRS enhancement were considered.
This paper reports on the analytical application of the oxidation reaction of [Os(bpy)3]2+ by Mn7+ (MnO4-). The present study developed a very simple, sensitive and selective spectrophotometric method for the determination of manganese in an acidic medium. Three analytical wavelengths were employed in the UV and visible regions at 290, 315 and 480 nm. Beer's law was obeyed up to a concentration of 330 ng ml-1 of Mn7+ at different wavelengths with regression equations 0.001 - 0.0042CMn, 0.001 + 0.0021CMn, and 0.001 - 9.34 × 10-4CMn at 290, 315 and 480 nm, respectively. Under the optimum conditions, the achieved detection limits were 0.72, 1.37 and 3.32 ng ml-1 at 290, 315, and 480 nm, respectively. In addition to the high sensitivity of the method (0.24 ng cm-2 at 290 nm, 0.45 ng cm-2 at 315 nm and 1.0 ng cm-2 at 480 nm), it can be used for the determination of manganese in the presence of a large number of anions and cations, since it tolerates most of the potential interferents. The relative standard deviation was 0.5% (n = 11) for 90 ng ml-1 manganese. The method was successfully applied to the determination of manganese in water from different resources.
Three simple spectrophotometric methods have been described for the assay of olanzapine in its pure and pharmaceutical formulations. The direct method (A) is based on the drug oxidation with excess of N-bromosuccinimide in acidic medium and the two indirect methods (B and C) are based on the oxidation of the drug with excess of N-bromosuccinimide and cerium(IV)sulfate, followed by the reaction of the unconsumed oxidants with celestine blue. The calibration graphs were linear over the range 10 - 120 µg mL-1 (method A), 0.5 - 6.0 µg mL-1 (method B) and 0.6 - 3.0 µg mL-1 (method C). After validation, the proposed methods were successfully applied to assay of olanzapine in its commercial tablets with mean percentage recoveries of 101.23 ± 0.10, 96 ± 0.10 and 94 ± 0.04%. The mechanism of olanzapine oxidation with N-bromosuccinimide was also proposed.
Current on-line solid-phase extraction methods combined with HPLC for shortening the clean-up operation are not suitable for simultaneously detecting compounds that have a wide variety of hydrophobicities. To solve these problems, we designed a new on-line sample preparation system. The system consists of an eluting pump, a mixing TEE connector, a 10-port 2-position valve and a solid-phase extraction precolumn. The eluate from the precolumn is diluted with a weak solvent from the HPLC at the TEE connection to load low hydrophobic compounds onto the analytical column. The proposed on-line sample preparation system was successfully applied to the simultaneous analysis of 21 pesticides in river water using LC/TOF-MS. In this method, the recoveries from river water samples were 67 to 126% (mean 83%), the reproducibility (CV%) was in the range from 1.1 to 11% (mean 5.6%), the calibration curve was linear in the range from 1 ppb to 500 ppb (r > 0.999) and the detection limits (S/N = 3) were in the range from 0.0034 ppb (daimuron) to 3.3 ppb (oxine-copper).
The solid-phase chemiluminescence analysis of gold on the surface of an anion-exchange resin was studied. A method for the fast determination of gold using flow injection was established. The anion-exchange resin was used as an adsorbent of gold ion in the form of AuCl4-. The cation-exchange resin was used for the on-line separation of cations in the matrix. To obtain the best results, the preconcentration and separation conditions, chemiluminescence conditions, interfering ions and their elimination conditions were optimized. The linear range of the calibration curve of AuCl4- is from 0 µg ml-1 to 5.00 µg ml-1. The detection limit of AuCl4- is 0.012 µg ml-1. The method has been used for the determination of gold in geological samples (standard ores). The results are in agreement with certified value of gold standard samples with relative standard deviation from 2.22% to 8.97%. Through the use of flow injection, the preconcentration and separation can be performed automatically.
Fog droplets in the atmosphere are first produced by the activation of cloud condensation nuclei (CCN), which are originally some ionic compound. Subsequently, the nuclei grow by vapor diffusion. Fog droplets are polluted through the activation process and successive diffusion growth and residence (post activation). We cannot distinguish the effects of the two pollution processes of natural fog water samples. We found that fog droplets can be produced artificially without CCN using an ultrasonic humidifier. Because the artificial fog droplets are not polluted by CCN, the movement of the fog droplets in natural air will take up some pollutants in the air. Consequently, the two pollution processes of fog (the activation of CCN and the post activation process) can be discriminated using data from field experiments. This sampling analytical method is extremely important for further research regarding fog, clouds and environmental chemistry.
This work assesses the use of modified natural natrolite zeolite as an adsorptive material for the separation and preconcentration of trace amounts of ions. In this work we investigated the potential of modified natural natrolite zeolite for the simultaneous separation and preconcentration of trace amounts of copper and zinc ions. We have developed a simple, rapid, selective, sensitive and economical method for the simultaneous separation and preconcentration of trace amounts of copper and zinc in an aqueous medium using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) as an analytical reagent. The sorption was quantitative in the pH range 7.5 - 9.5, whereas quantitative desorption occurred instantaneously with 5.0 mL of 2 mol L-1 nitric acid. Linearity was maintained between 0.05 - 6.0 µg mL-1 for copper and 0.02 - 1.5 µg mL-1 for zinc in the final solution. Ten replicate determinations of 1.0 µg mL-1 copper and 0.5 µg mL-1 zinc in a mixture gave mean absorbances of 0.1687 and 0.2788 with relative standard deviations of ±1.2% and ±1.3%, respectively. The detection limits were 0.03 ng mL-1 for Cu(II) and 0.006 ng mL-1 for Zn(II) in the original solution (3 σbl/m). Different parameters, such as the effect of the pH, flow rate, breakthrough volume and interference of a large number of anions and cations, were studied and the proposed method was used for the determination of these metal ions in water as well as standard samples (e.g. Nippon Keikinzoku Kogyo (NKK) CRM, No. 916 and No. 920 aluminum alloy, National Institute for Environment Studies (NIES) No. 1 pepperbush and NIES No. 2 pond sediment). The determination of these metal ions in standard samples showed that the proposed method has good accuracy (recovery > 97%).
A method for the determination of Ti and V using inductively coupled plasma atomic emission spectrometry (ICP OES) in Ziegler-Natta polymerization catalysts is proposed. The concentrations of both Ti and V are efficiently determined after catalyst acid digestion with a mixture of HNO3 + HCl + HF and heating (160°C for 6 h) or with 10% (v/v) H2SO4 and heating (160°C for 6 h) or with 10% (v/v) H2SO4 and sonication (during 2 min). The V and Ti detection limits are 0.002% and 0.08%, respectively, using 0.20 g of catalyst sample in 50 ml. The method is validated by a comparison with the Rutherford backscattering spectrometry (RBS) technique. In this case, catalyst samples are only pressed as pellets before analyte determination. Despite the fact that both the V and Ti concentrations cannot be determined individually by means of RBS, because the atomic numbers of Ti and V are very close, the sum of the V and Ti contents is in accordance with that attained by means of ICP OES. According to scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) it is observed that the Ti distribution on the catalyst grain is not homogenous.
A flow system was developed for the determination of total mercury concentration in fish samples by cold vapor atomic absorption spectrophotometry (CVAAS), based on the multicommuted flow injection analysis (MCFIA) approach. The system uses independently controlled solenoid valves for the introduction of reagents and samples. When not injected, solutions were recirculating to the reservoir bottles, in this way reducing the waste produced by the analytical system and also the sample consumption. Results were compared to those obtained by the reference flow injection procedure. Accuracy was also assessed by recovery studies using a certified reference material as well as spiked samples; recovery percentages in the range of 90.7% to 99.8% were found. The repeatability of the method was better than 6.0% (RSD, n = 10). A limit of detection of 4.8 µg of mercury per kg of fresh fish sample was achieved. The total waste produced was reduced to 30% of that from the reference flow injection CVAAS procedure.
A coated-wire ion-selective electrode (CWISE), based on a Schiff base as a neutral carrier, was successfully developed for the detection of Pb(II) in aqueous solution. CWISE exhibited a linear response with a Nernstian slope of 29.4 ± 0.5 mV/decade within the concentration range of 1.0 × 10-5 - 1.0 × 10-1 M lead ion. CWISE has shown detection limits of 5.0 × 10-6 M. The electrode exhibited good selectivity over a number of alkali, alkaline earth, transition and heavy metal ions. This sensor yielded a steady potential within 10 to 20 s at a linear dynamic range. The electrode was suitable for use in aqueous solutions in a pH range of 2.0 to 5.0. Applications of this electrode for the determination of lead in real samples and as indicator electrode for potentiometric titration of Pb2+ ion using K2CrO4 are reported.
A wax-impregnated carbon paste electrode with mercury oxalate as the bulk modifier is found to be suitable for the determination of heavy metal ions by differential pulse anodic stripping voltammetry. The contents of binder and modifier have been optimized, until they showed low background current and easy renewability. The bulk-modified electrode is applied for the simultaneous determination of Zn, Cd, Pb and Cu in medicinal plants and Ayurvedic tablets (Liv 52). The results obtained have been validated with HMDE and AAS and are found to be comparable.
Two novel potentiometric sensors that are highly selective to Hg2+ ions are described. These are based on the use of 5,5′-dithio-bis(2-nitrobenzoic acid) (DTNB) and tricyclazole (TCZ) as neutral carriers in plasticized poly(vinyl chloride) membranes. Fast Nernstian responses are obtained for Hg2+ ions over the concentration ranges 7.0 × 10-6 - 1.0 × 10-2 and 7.7 × 10-6 - 1.0 × 10-2 mol l-1 at pH 1.8 - 3.3 with lower detection limits of 5.0 × 10-6 and 5.6 × 10-6 mol l-1 (∼1 µh ml-1) and calibration slopes of 30.0 and 29.7 mV decade-1 with DTNB- and TCZ-based membrane sensors, respectively. Validation of the assay method reveals good performance characteristics, including long life span, good selectivity for Hg2+ ions over a wide variety of other metal ions, long term response stability, and high reproducibility. Applications for direct determination of mercury in hazardous wastes including dental amalgam, mercury bulbs, and fluorescent lamps give results with good correlation with data obtained using cold vapor atomic absorption spectrometry.
A fast, convenient and sensitive method of capillary zone electrophoresis (CZE) and indirect UV detection was proposed for the determination of 16 amino acids. p-Aminobenzoic acid (PAB) was selected as a background electrolyte (BGE). An isolated cell included a BGE buffer part and an electrode buffer one, which were jointed with a glass frit. The isolated cell can prevent PAB from the electrode reaction and improve the stability of the detection baseline. The separation conditions of amino acids were investigated, such as different BGEs, BGE concentration, buffer pH and electroosmotic flow (EOF) modifiers. Under the selected separation conditions, 14 amino acid peaks could be separated in 12 min. The detection limits of the amino acids were in the range of 1.7 - 4.5 µmol/L. The isolated cell is suitable for reagents reacting on the electrodes in capillary electrophoresis. The proposed method has been successfully applied to the determination of the amino acids in tobacco samples.
The traditional method for linear calibration can estimate the confidence intervals of calibration lines from a set of experimental data for a single calibration line. However, the following situations, often encountered in laboratories, are out of reach of the method, since the concentrations of the standard solutions are not independent of each other: (A) a standard solution is diluted from a more concentrated one in a stepwise way (stepwise dilution); (B) every standard solution for a calibration experiment is prepared from a stock solution, but the stock solution is newly prepared for each calibration (separate dilution with the variable concentration of the stock solution). This paper puts forward a theory to calculate the confidence intervals of calibration lines in the above situations. Analyses made up of sample weighing, dilution, HPLC measurement and calibration with the linear least-squares fitting are taken as examples. The proposed theory is numerically compared to the traditional method.
For the purpose of low cost and sensitive electrochemical detection of 17 β-estradiol (E2), a multi-wall carbon nanotube (MWNT)-Nafion modified electrode was fabricated. The MWNT modified electrode shows enhancement for the anodic peak current of E2 compared with the value obtained using a bare electrode. The anodic peak current measured by square wave voltammetry after 5 min open-circuit accumulation was proportional to the concentration of E2 over the range of 2.5 × 10-7 to 10 10-6 M, and a detection limit of 1 × 10-8 M was obtained.
Uptakes of benzene and 12 alkylbenzenes (from toluene to n-pentylbenzene including xylene and trimethylbenzene isomers) by both strong acid cation (Dowex 50W-X4 and X8) and strong base anion (Dowex 1-X4 and X8) exchange resins have been studied in aqueous solutions at 25°C; their distribution constants (K) have been determined. The relationship between the octanol-water partition coefficient (Kow) and the resin affinity for solutes has been analyzed. The K values of benzene and alkylbenzenes were larger than the K values of aliphatic hydrocarbons expected from the Kow values. While the K value was increased with the alkyl chain length, no further increase in the K value was observed for n-butylbenzene and n-pentylbenzene.
The relationship between the periodical bubble forming and the oscillatory change in the dissolved oxygen (DO) concentration in a catalase-hydrogen peroxide system was studied. Photographs of the bubbles and the responses from the DO electrode indicated that large bubbles were generated periodically, and that the DO profile depended on the geometrical relationship between the electrode and the bubbles.
In a dye-binding method using a pH indicator, color development has reportedly been affected by the kind of buffer solution used in the color reagent. This phenomenon was analyzed by using a calculation based on the assumption that the anion of the buffer solution also reacts with protein. Color development decreases with increases in the anion concentration of the buffer solution and in the equilibrium constant of the reaction between the anion and protein. The differences in color development due to the kind of buffer solution can be attributed to differences in the equilibrium constant of the reaction forming the anion-protein complex and to the concentration of the anion between the buffer solutions.
The possibility was investigated by using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) as the chelating reagent for separation and preconcentration of manganese(II) by cloud point extraction (CPE) and subsequent determination by flame atomic absorption spectrometry (FAAS). The effects of experimental conditions such as pH, concentration of chelating agent and surfactant, equilibration temperature and time on cloud point extraction were studied. Under the optimum conditions, preconcentration of 10 ml of sample solution permitted the detection of 1.45 ng mL-1 of manganese with an enrichment factor of 20. The proposed method was applied to the determination of trace manganese in water samples with satisfactory results.